Amine oxide-amphoteric surfactant-cationic surfactant-oil containing hair conditioning shampoo

ABSTRACT

A HAIR CONDITIONING SHAMPOO FOR IMPROVING THE COMBING PROPERTIES AND LUSTER OF HAIR WASHED THEREIN COMPRISING A SINGLE PHASE AQUEOUS DETERGENT COMPOSITION SUITABLE FOR SHAMPOOING HAIR WHICH CONTAINS A HIGHER ALKYL AMINE OXIDE, AN AMPHOTERIC SURFACTANT, A CATIONIC SURFACTANT, DAND AN OIL FROM THE GROUP CONSISTING OF MINERAL OIL, VEGETABLE OIL, ANIMAL OIL, AND SYNTHETIC OIL, IN PROPER PROPORTIONS.

3,808,311 AMINE OXIDE-AMPHOTERIC SURFACTANT- CATIONIC SURFACTANT-OILCONTAINING HAIR CONDITIONING SHAMPOO Frank Wesley Olson, Jr., PomptonPlains, and Karl Hutcheson Roberts, Flemington, NJ., assignors to C01-gate-Palmolive Company, New York, N.Y.

No Drawing. Continuation-impart of abandoned application Ser. No.845,586, July 28, 1969. This application June 4, 1970, Ser. No. 43,599

Int. Cl. A61k 7/06 US Cl. 424-70 4 Claims ABSTRACT OF THE DISCLOSURE Ahair conditioning shampoo for improving the combing properties andluster of hair washed therein comprising a single phase aqueousdetergent composition suitable for shampooing hair which contains ahigher alkyl amine oxide, an amphoteric surfactant, a cationicsurfactant, and an oil from the group consisting of mineral oil,vegetable oil, animal oil, and synthetic oil, in proper proportions.

This application is a continuation-in-part of copending application Ser.No. 845,586 filed July 28, 1969, now abandoned.

The present invention relates to a hair conditioning shampoo forimproving the combing properties and luster of all colors of hair whichcomprises a single phase aqueous detergent composition suitable for usein shampooing hair which contains a higher alkyl amine oxide, anamphoteric surfactant, a cationic surfactant, and an oil from the groupconsisting of mineral, vegetable, animal, and synthetic oils in properproportions.

There have been suggestions in the prior art to use mineral oil inchampoos. One such suggestion proposed the use of up to about 3% ofmineral oil in a shampoo containing sulfonates of fatty oils as thesurfactant but, in effect, condemned this proposal on the ground that itis difficult to wash out. Another suggestion was to form a two phaseshampoo by the use of at least 5% liquid oil material in an aqueousdetergent composition in which an oil phase floats on the top of anaqueous phase as a sharply defined clear, separate layer and anessential ingredient in this composition was an emulsion breaker insuflicient proportion to insure the rapid and sharp separation of thetwo phases after they had been emulsified by shaking. In general, theconsumers reaction to such shampoo has not been favorable.

Shampoos containing amine oxides, amphoteric detergents and cationicdetergents have been proposed for hair conditioning effects but it hasbeen found that the degree of hair conditioning efifects obtainable bythe use of these ingredients is limited and that when hair is combed wetafter shampooing with such a composition an undesirable foarrllJ isproduced which is particularly noticeable on the com It has now beendiscovered that improved combing properties, particularly the absence orsubstantially reduced amount of foam produced in wet combing, animproved degree of hair conditioning and an observable and highlydesirable shine or luster and other properties mentioned hereinafter canbe imparted to hair of all colors by shampoo compositions which containproper proportions of a higher alkyl amine oxide, an amphotericsurfactant, a cationic surfactant and a non-volatile oil from the groupconsisting of mineral, vegetable, animal, and synthetic oils, andmixtures thereof.

The mineral oil used in compositions made in accordance with theinvention may be any oil that dissolves in United States Patent 0"3,808,151 l Patented Apr. 30, 1974 the detergent composition insuflicient proportions to function as described herein. The preferredoil is a mineral oil, and it may be a light to heavy hydrocarbon oil butis preferably a light mineral oil such as a water-clear, completelysaturated, mineral oil having a Saybolt viscosity of about 50-80,desirably 55-65 cps. at F., a specific gravity compared with water whenthe oil and water are at 25 C. of 0.831 to 0.871, a flash point of 280minimum and a fire point of 305 F. minimum, as obtained by the Clevelandopen cup method. The preferred mineral oil may be replaced in whole orpart by olive oil or other comparable nonor semi-drying vegetable andanimal oils having an iodine number less than 105, such as linseed oil,castor oil, cotton seed oil, safilower oil, almond oil, peanut oil,coconut oil, soya bean oil, sesame oil, avocado oil, and mineral oilsoluble lanolin derivatives, such as lanolin esters, lanolin alcoholsand ethylene oxide adducts thereof. Synthetic oils, i.e., esters offatty acids having from about 10 to 20 carbon atoms such as isopropylmyristate, palmitate and stearate may also be used.

The proportion of oil, whether mineral, vegetable, animal or syntheticin the composition should be sufficient to produce the desired effect,usually at least about 0.5% but not enough to produce a separate phaseon standing. 'In other words, the oil should be taken into the aqueoussystem', whether by dissolution or otherwise, so as to appear to the eyeto be a single phase. The upper limit may vary, depending on the natureof the oil and the ingredients and proportions of the aqueous system.The upper limit is less than 5%, often less than 3%, and an effectivemaximum is about 2%.

In the description and claims where percentages are given, they are byweight of the entire composition.

The suitable higher alkyl amine oxides are those having the formula:

where R is a higher alkyl group containing an average of about 12 to 20carbon atoms, preferably about 13 to 16 carbon atoms, and R and R eachrepresent a radical selected from the group consisting of alkyl andhydroxyalkyl groups having one to four carbon atoms or R and R togetherwith the oxygen linked nitrogen form a heterocyclic morpholino group,e.g.,

CHPCHI Typical higher alkyl groups which may be present include decyl,lauryl, myristyl, cetyl, stearyl, eicosyl or other higher alkyl groupsof about 10-20 carbon atoms, derived for example from tallow,hydrogenated tallow, coconut oil, etc. The amine oxides in which theaverage number of carbon atoms in the higher alkyl groups is about 15have given compositions whose foams (produced during shampooing of thehair) have a creamier appearance, with a smaller bubble size. Mostpreferably both R and R are methyl groups, but other radicals, e.g.,ethyl hydroxyethyl or hydroxypropyl, may be used in place of one or bothmethyl groups.

The water-soluble, ampholytic or amphoteric detergents which can be usedin the compositions of the invention generally contain a hydrophobicalkyl group of about 10 to 20 carbon atoms attached directly orindirectly to at least one cationic group, e .g., non-quaternarynitrogen, quaternary nitrogen, or quaternary phosphorous, and at leastone anionic water-solubilizing group, e.g., carboxylic, sulfonic,sulfuric, or phosphonic acids or salts thereof, in their molecularstructure. The alkyl group may be straight chain or branched, and thespecific cationic atom may be part of a heterocyclic ring.

Examples of suitable ampholytic detergents include the alkylbeta-aminopropionates, R N(H)C H COOM; the alkylbeta-iminodipropionates, R N(C H COOM) and the long chain imidazolederivatives sold under the trade name Miranol having the followingformula:

wherein R is an alkyl group of about to 20 carbon atoms, R is analkylene or hydroxyalkylene group containing l to 4 carbon atoms and Mis a water-soluble cation, e.g., alkali metal, ammonium oralkylolammonium. The higher alkyl group of the aminopropionates andiminodipropionates may be, for example, derived from coco fatty alcohol,lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, orblends of such alcohols; whereas, the higher alkyl group of theimidazole derivative is derived from coconut oil or tallow. Preferreddetergents are sodium N-lauryl beta-aminopropionate, disodium n-laurylbeta-iminodipropionate, and the sodium salt of 2 lauryl cycloimidiuml-hydroxyl, l-hydroxy ethanoic acid, l-ethanoic acid.

Other suitable amphoteric, imidazole detergents have the followingstructure:

wherein R is a higher acyclic group of 7 to 17 carbon atoms and M is awater-soluble cation, e.g., sodium, potassium, ammonium, and mono-, diortri-alkylammonium. The acylic groups may be derived from coconut oilfatty acids (a mixture of fatty acids containing 8 to 18 carbon atoms),lauric fatty acid, and oleic fatty acid, and alkyl groups of 7 to 17carbons are preferred acyclic groups. Such detergents can be prepared bydehydrating the reaction product of a higher fatty acid and ahydroxyalkyl alkylene polyamine, e.g., beta-hydroxyethyl ethylenediamine as described in US. Pat. 2,267,965, and then reacting theresultant imidazoline with acrylic acid as shown in French Pat.1,412,921 followed by neutralization.

Other suitable amphoteric detergents are the sultaine and betaine typeshaving the following general structure:

wherein R is an alkyl group containing about 8 to 18 carbon atoms, R andR are lower alkyl groups containing 1 to 3 carbon atoms, R; is analkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms,and X is an anion selected from the group consisting of SO (sultaine)and COO=(betaine). Preferred compounds are l-(myristyl dimethylammonio)acetate and 1- (myristyl dirnethylammonio 2-hydr0xypr0pane-3-sulfonate.

With the exception of the internally neutralized betaine and sultaineamphoteric detergents, as stated above, the foregoing amphotericdetergents are usually applied in the sodium, potassium, alkylolammonium or other salt form. It is preferred to use those amphotericdetergents which dissolve and foam readily in water at the pH of 8.8-9.6and the most preferred amphoteric detergents are the higher alkylbeta-aminopropionate salts and the higher alkyl beta-iminodiproprionatesalts.

Cationic detergents which may be used are the quaternary ammoniumcompounds having at least one long chain hydrophobic radical, e.g.,alkyl radicals of 10 24 carbon atoms, in their molecular structure. Thehigher alkyl group may be directly attached to the quaternary nitrogenor indirectly attached thereto through an imidazole group or anamidopropyl group. Suita ble quaternary ammonium salts are selected fromthe group consisting of higher alkyl quaternary ammonium salts havingthe following formulas:

1 1- 3 X", and

wherein R is a higher alkyl or alkenyl group containing an average of 10to 24 carbon atoms, R is an alkyl or hydroxyalkyl group of l to 3 carbonatoms, R is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or abenzyl group, and X is an anion selected from the group consisting ofchloride, methosulfate, bromide, phosphate, dialkyl phosphate, andacetate. Preferred cationic compounds are Z-stearyl, l-methyl orl-hydroxyethyl, 1- stearylamido-ethyl imidazolinium methosulfate andtallowyl amidopropyl, dimethyl, hydroxyethyl ammonium chloride (tallowyldescribes the mixture of C to C fatty acids obtained from tallow).

The quaternary ammonium compound is preferably one which. is stable inaqueous solution or dispersion at pH 9 at room temperature and morepreferably stable for at least a month at pH 9 at F. The preferredquaternary ammonium compounds are free of ester linkages unstable underthe foregoing conditions. (Preferably the other detergent components,and the entire composition, should meet this same stabilityrequirement.) The water-soluble quaternary ammonium compound is mostusually supplied as a chloride or methosulfate Best results have beenthus far obtained with compositions whose proportions are in thefollowing ranges (the ranges being in percent by weight of the shampoocomposition): water-soluble quaternary ammonium detergent surfactantabout 0.1-10%, preferably about 1-6%; water-soluble amphoteric detergentsurfactant about 2- 20%, preferably about 3-12% (calculated as theacidic form of the amphoteric material); water-soluble amine oxidedetergent surfactant about 118%, preferably about 4-15 Generally thetotal amount of the detergents in the mixture is in the range of about1230%, preferably about 1525%. It will be appreciated, of course, thatthe compositions may be supplied in more highly concentrated form, forsubsequent dilution with water.

The pH of the composition should be at least about 5, generally above 7,desirably about 8.8 to 9.6, preferably about 8.9 to 9.2. When the pH isbelow 7, M as defined above may include hydrogen. The pH may be adjustedto the level desired by the use of an acidic and/or an alkalinematerial. For this purpose acidic materials such as citric acid andbasic materials, e.g., a water-soluble substantially non-volatile aminesuch as an alkanolamine, preferably tri-ethanolamine, may be used forthis purpose, as may inorganic bases such as sodium hydroxide orpotassium hydroxide. Citric acid also serves as a sequestering andbuffering agent and is frequently added for this purpose even if notneeded for pH adjustment. Generally speaking minor proportions, up to amaximum of about 2%, of each of these ingredients is sufiicient toobtain the desired pH adjustment. Typically the pH of the compositionremains substantially constant on considerable dilution with water; inone typical case the pH (measured electrically) was 9.05 at 20%concentration, 9.01 at 9.00 at 5%, 8.98 at 2% and 8.97 at 1%concentration.

Compositions of a wide range of viscosities may be produced from thecombination of the foregoing ingredients. It is often desirable to addviscosity-adjusting ingredients. As viscosity-increasing materials theremay be used long chain fatty amides, e.g., a monoethanolamide,diethanolamide or dimethylamide of a fatty acid of about 10 to 16 carbonatoms such as lauric-myristic monoethanolamide or diethanolamide. Asviscosity decreasing ingredients which also serve to lower the cloudpoint of the composition there may be used water-soluble solvents, suchas monohydric alcohols containing 2 to 3 carbon atoms, polyhydricalcohols, e.g., propylene glycol or ethoxylated poly-propylene glycol orlower alkyl ethers of such glycols. The proportion of such ingredientsis generally less than 5% of the total composition, e.g. about /24%.

Water-soluble protein may also be present in the compositions. Thisingredients in the compositions described above gives improved curlretention to the shampooed hair, while substantially retaining orimproving the other desirable effects previously discussed. Chemically,this ingredient is a low molecular weight polypeptide obtained byhydrolysis of protein materials such as human and animal hair, horns,hides, hoofs, gelatin, collagen, and the like. During hydrolysis theproteins are radually broken down into their constituent polypeptidesand amino acids by prolonged heating with acids, e.g., sulfuric acid, oralkalis, e.g., sodium hydroxide, or treatment with enzyme, e.g.,peptidases. In hydrolysis, high molecular weight polypeptides are formedfirst and as hydrolysis proceeds these are converted progressively tosimpler and simpler polypeptides, to tripeptides, dipeptides, andfinally to amino acids. It is obvious that the polypeptides derived fromproteins are complex mixtures and in practice the average molecularweight of the hydrolysis will vary from 120 (amino acids) to about20,000. All satisfactory hydrolyzed polypeptides are characterized bywater solubility. In compositions which contain soluble protein it ispreferred to use hydrolyzed collagen of such low molecular weight as tobe completely soluble in water, nongelling, and non-denaturing with anaverage molecular weight below 15,000, preferably in the range of about500 to 10,000. The amount of protein used is preferably in the range ofabout /23% most preferably about 1 to 2%.

It is desired in many cases to color the shampoo composition a desirableshade such as yellow, green, amber, blue, etc. For this purpose anysuitable dyes may be incorporated in the solution. For example, D & Cyellow No. 1, in a 1% solution, may be added to a shampoo composition ofthe above type at a level of about 0.05% to produce a desirable yellowcolor. A very attractive green color can be obtained by using about 0.2%FD & C yellow No. 5 1% solution) and a 0.1% FD & C blue No. 1 (1%solution). An amber color is obtained by using about 0.075% D & C orangeNo. 4 (1% solution) with 0.025% red No. 2 (0.1% solution). An attractiveblue color can be obtained by using 0.25% FD & C blue No. 1 (1%solution) and 0.050% D & C red No. 19 (0.1% solution).

Where dyes are added to the composition it is preferred to include acolor preservative, e.g., a compound which absorbs ultraviolet light,e.g., a mixture of 2,2- dihydroxy-4,4-dimethoxy benzophenone and othertetrasubstituted benzophenones, referred to hereafter as Preservative X,and 2,4-dihydroxy benzophenone, referred to hereafter as Preservative Y,and mixtures thereof. These materials are very effective in smallproportions and in general about 0.025% adequately protects thecomposition from color change on exposure of the composition to lightduring storage and use. They may be used, however, within broader rangesof about 0.01 to 0.1% Preservative X is preferred for all the abovecolors except blue for which Preservative Y is preferred.

It is also preferred to include a material which inhibits bacterialgrowth in the detergent compositions, e.g., formaldehyde USP, which iselfective when about 0.1% is present. Other preservatives may also beused.

In general it is preferred to include a perfume of a suitable type andodor in the composition for its cosmetic appeal to the user. Perfume maybe present within the range of 0-2%.

The liquid vehicle in which the foregoing ingredients are carried,primarily in solution, is water which may be replaced in part by a loweraliphatic monohydric alcohol, e.g., ethyl, propyl, and isopropylalcohols. In some formulations lower aliphatic polyhydric alcohols suchas propylene glycol and glycerine may be used. Alcohol may be presentwithin the range of about 0-10% but never in such high proportion withreference to the oil content that a separate oil phase is formed. Inmaking up the composition it is preferred to use deionized water so asto avoid discoloration and other adverse effects of the water hardness.

Examples I, II and HI set forth satisfactory compositions of hairconditioning shampoos formulated in ac cordance with the presentinvention.

Percent Example I II III Myristyl dimethyl amine oxide 12. 0 12. 0 6. 0

allow amidopropyl dimethyl hydroxy-ethyl ammonium chloride 3. 0 3. 0 0.5 N-lauryl-myristyl beta-alaninm 3. 0 3.0 8. 0 Lauric-myristicdiethanolamide 3. 0 4. 0 1. 6 Soluble protein 1. 5 1. 5 Citric acid(anhydrous) 0. 25 0. 25 0. 25 Mineral oil-extra light 0. 5 2. 0 Oliveoil 1. 6 Caustic soda (to adjust to pH 9) q.s q.s. q.s Deionlzed water(with and without additives such as dyes, perfumes stabilizers,preservatives) q.s. q.s. q.s

Total 100.00 100. 00 100. 00

The shampoos of the present invention are quite compatible withmaterials used on hair, particularly resintype hair sprays, and they areentirely suitable for use on hair that has been damaged by bleaches,hair waving and straightening compositions, exposure to sun and seawater, etc. On combing the wet hair after shampooing there is either noobservable foam on the comb or, if present at all, the amount thereof isgreatly reduced as compared with the amount produced by a shampoo of thesame formulation without the oil. The hair conditioning effect is alsoraised to a new level above that obtainable in these compositionswithout it.

The hair conditioning effect of a shampoo is difficult to measureaccurately because it is a combination of a number of properties orcharacteristics of the hair after it has been shampooed, both in wetcondition and dry. A

7 useful but somewhat arbitrary scale of hair conditioning effects is asfollows:

Value on scale Characteristics of hair Those obtained by washing with ashampoo based on an anionic sulfate and/or sulfonate only. There are nogood combing effects dry or wet. Snarls and snags are hard to comb out,there is a raspiness on dry combing and the dry combed hair is stronglycharged with static electricity.

1 Those obtained by washing with a shampoo having some ingredientspresent that make wet and dry combing easier than without suchingredients but still leave dry combed hair electrified.

2 Those obtained by washing with a shampoo havlng further ingredientspresent that eliminate static on dry combing but do not entirelyeliminate snarls.

3 Those obtained by washing with a shampoo such as Examples I and 11without oil which leaves the washed hair fairly soft and easy to combwet or dry without snarls and without static on dry combing.

4 Those obtained by washing with a shampoo such as Examples 1, II andIII which leaves the hair still easier to comb because it has greatersoftness and weight and is more shppery than value 3.

What is claimed is:

1. A single phase liquid shampoo for improving combing properties andluster of hair consisting essentially of 1 to 18% by weight of awater-soluble higher alkyl amine oxide having the formula R3 wherein Ris a higher alkyl group containing an average of about 12 to 20 carbonatoms and R and R each represent a member selected from the groupconsisting of alkyl and hydroxyalkyl having one to four carbon atoms orR and R together with the oxygen linked nitrogen form a morpholinogroup; 220% byweight of a watersoluble amphoteric surfactant having ahydrophobic alkyl group of about 10 to 20 carbon atoms attached directlyor indirectly to a non-quaternary nitrogen or quaternary nitrogen, andat least one anionic water-solubilizing group selected from the groupconsisting of carboxylic and sulphonic acids or salts thereof in itsmolecular structure, said salt being selected from the group consistingof sodium, potassium, ammonium, and alkylolammonium; 0.5-10% by weightof a water-soluble cationic quaternary ammonium surfactant having along-chain hydrophobic radical of 10 to 24 carbon atoms directly orindirectly attached to the quaternary nitrogen; and at least about 0.5%and less than 5% by weight of a non-volatile oil selected from the classconsisting of a mineral oil, a nonand semi-drying vegetable oil, anisopropyl ester of a C C fatty acid, and mixtures thereof in an aqueousvehicle containing 010% by weight of a lower monohydric or polyhydricalcohol containing from 2 to 3 carbon atoms; the total content of saidamine oxide, said amphoteric surfactant, and said cationic detergentbeing about 1230% by weight of said shampoo.

2. A liquid shampoo according to claim 1 wherein said oil is extra lightmineral oil or olive oil and is present in an amount from 0.5 to 2% byweight.

3. A liquid shampoo in accordance with claim 1 which contains inaddition from /2 to 3% by weight of a water-soluble non-gelling proteinmaterial selected from the group consisting of hydrolysis products ofhuman and animal hair, horns, hides, hoofs, gelatin, and collagen, andhaving a molecular weight in the range of about 500 to 10,000.

4. A single phase liquid shampoo for improving combing properties andluster of hair consisting essentiall of 6 to 12% by weight of C -C highalkyl dimethyl amine oxide, 0.5 to 3% by weight of tallowyl amidopropyldimethyl hydroxyethyl ammonium chloride, 1.6 to 4% by weight oflauric-myristic diethanolamide, 3 to 8% by weight of N-lauryl-myristylbeta-alanine, 0.5 to 2% by weight of oil selected from the classconsisting of extra light mineral oil and olive oil, and water.

References Cited UNITED STATES PATENTS 2,770,599 11/1956 Henkin 252 1173,086,943 4/1963 Lang 252 152 3,098,794 7/1963 Dohr et a1. 424- x3,152,181 10/1964 Shapiro et a1. 424-70 X 3,179,595 4/1965 Olson 2521183,533,955 10/1970 Pader et al. 424-40 X FOREIGN PATENTS 1,519,951 2/1968France 424- 70x OTHER REFERENCES Keithler, The Formulation of Cosmeticsand Cosmetic Specialties, Drug and Cosmetic Industry, New York, N.Y.(1956), pp. 204-205.

JEROME D. GOLDBERG, Primary Examiner V. C. CLARKE, Assistant ExaminerU.S. Cl. X.R.

252-Dig. 2, 7, 13, 14, 542, 547, 153; 424-4559

